CN109133191B - Three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material and preparation method thereof - Google Patents
Three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN109133191B CN109133191B CN201811082317.9A CN201811082317A CN109133191B CN 109133191 B CN109133191 B CN 109133191B CN 201811082317 A CN201811082317 A CN 201811082317A CN 109133191 B CN109133191 B CN 109133191B
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Abstract
A three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material and a preparation method thereof are disclosed, wherein cobalt acetate tetrahydrate, thioacetamide and ethylene glycol are added into a container to obtain a solution A; dissolving dopamine hydrochloride in ultrapure water to obtain a solution B; after the solution B is added into the solution A, carrying out the solvothermal reaction at the temperature of 175-185 ℃ in a phase reaction instrument in a uniform-speed rotating state; after the solvothermal reaction is finished, washing and drying are carried out, so that the product obtained by the solvothermal reaction method is small in particle size, has a large specific surface area and is integrally in a three-dimensional porous spherical structure when used as a negative electrode material in a sodium ion battery, and Na is reduced+The migration distance of the electrolyte increases the electrolyte and Na in the electrode material+The contact area of the electrode is larger, more active sites are provided, and the electrochemical performance is good.
Description
Technical Field
The invention relates to a three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material and a preparation method thereof, which are applied to the sodium ion battery cathode material and belong to the field of electrochemistry.
Background
Lithium ion batteries have become one of the most interesting energy storage devices in recent years due to their advantages of light weight, small size, high operating voltage, high capacity, long cycle life, etc. Due to the large scale use, the storage of lithium resources on earth is also facing depletion. And the sodium resource has large storage capacity on the earth, abundant resources and easy acquisition, so the preparation cost of the sodium resource is lower than that of a lithium ion battery. Meanwhile, the lithium ion battery has many similarities in properties with the lithium as the first main group element in the periodic table, and the sodium ion battery gradually becomes a research hotspot in recent years due to the characteristics of rich raw material reserves, low price, environmental friendliness and the like, and is considered as an ideal choice of the next generation of energy storage and power batteries [ Miao Yan, Liu xing Jiang.
The metal sulfide with the nano structure is used as a novel energy storage material and has good electrochemical performance. Cobalt sulfide can form a variety of compounds due to the different numbers of cobalt and sulfur atoms in a given amount. Wang et al successfully synthesized CoS with hierarchical flower-like structure by solvothermal method1.097At 5mA/cm-2The specific capacity is up to 555F/g-198% after 2500 cycles of circulation and exhibits excellent rate capability [ Q.Wang, L.Jiano, H.Du, J.Yang, Q.Huan, W.Peng, Y.Si, Y.Wang, H.Yuan.factor synthesis and super-performance superior ] J.Wang].CrystEng Comm2011,13:6960]. At present, cobalt sulfide-based materials, especially Co9S8And the method is applied to the field of photo/electro-catalysis to a great extent, most of synthesis means have more operation steps, and the adopted raw materials are not easy to obtain.
Disclosure of Invention
The invention aims to provide a three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material which is simple in reaction process, low in temperature, easy to control and free of large-scale equipment and harsh reaction conditions, and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material comprises the following steps:
1) adding cobalt acetate tetrahydrate, thioacetamide and ethylene glycol into a container, and stirring to obtain a pink turbid solution A;
2) dissolving dopamine hydrochloride in ultrapure water, and stirring to obtain a solution B;
3) adding the solution B into the solution A, uniformly dispersing by ultrasonic, and carrying out solvothermal reaction in a homogeneous phase reactor at the temperature of 175-185 ℃ in a uniform rotation state; and after the solvothermal reaction is finished, washing and drying to obtain the three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material.
The further improvement of the invention is that the mass ratio of the cobalt acetate tetrahydrate to the thioacetamide in the step 1) is (0.8-1.2): (0.2-0.5); the ratio of cobalt acetate tetrahydrate to ethylene glycol is 0.8-1.2 g: 35-45 mL.
The further improvement of the invention is that the rotation speed of stirring in the step 1) is 600-680 r/min, and the time is 55-65 min.
The further improvement of the invention is that the ratio of the dopamine hydrochloride to the ultrapure water in the step 2) is 15-20 mg: 15-25 mL.
The invention further improves that the mass ratio of the cobalt acetate tetrahydrate to the dopamine hydrochloride in the step 3) is (0.8-1.2) g: (15-20) mg.
The invention is further improved in that the ultrasonic time in the step 3) is 20-30 min.
The invention is further improved in that the rotation speed of the uniform rotation in the step 3) is 5-15 r/min.
The invention further improves that the solvothermal reaction time in the step 3) is 22-26 h.
The further improvement of the invention is that the drying temperature in the step 3) is 60 ℃ and the time is 11-13 h.
A three-dimensional pure-phase cobalt sulfide nanoparticle sodium ion battery cathode material is composed of a three-dimensional hollow spherical structure with the average diameter of 0.5-0.8 mu m, wherein the three-dimensional spherical structure is formed by self-stacking nanosheets with the uniform thickness of 20 nm.
Compared with the prior art, the invention has the following specific beneficial effects:
(1) the raw materials used in the invention are common materials, are cheap and easy to obtain, have low cost, do not need post treatment, are environment-friendly and are suitable for large-scale production;
(2) the preparation method has simple process, and the product yield is close to 100 percent;
(3) the cobalt sulfide product prepared by the invention is Co9S8The particle size is in nano scale, the particle size has larger specific surface area, the whole body is in a three-dimensional porous spherical structure, the pores provide a buffer area for volume expansion generated in the charge and discharge process, the structure of the material becomes more stable, and meanwhile, Na is reduced+The migration distance of the electrolyte increases the electrolyte and Na in the electrode material+The contact area of the anode material can provide more active sites, and the rate capability of the anode material can be improved;
(4) in the process of synthesizing the three-dimensional self-assembly structure, no template agent or surfactant is introduced, the whole self-assembly process is controlled by the self-template action of reaction raw materials, and the reaction process is easy to control.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product prepared in example 1 of this invention.
FIG. 2 is a scanning electron micrograph of a product prepared according to example 1 of the present invention.
FIG. 3 is a high power scanning electron micrograph of the product prepared in example 1 of the present invention.
Fig. 4 is a diagram of the electrochemical performance of the product prepared in example 1 of the present invention as a negative electrode material of a sodium ion battery.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The invention comprises the following steps:
1) taking 0.8-1.2g of cobalt acetate tetrahydrate, 0.2-0.5g of thioacetamide and 35-45ml of ethylene glycol, putting the three raw materials into a beaker, and stirring by using magnetic force to obtain pink turbid solution A;
2) dissolving 15-20mg of dopamine hydrochloride in 15-25mL of ultrapure water, and stirring to fully dissolve the dopamine hydrochloride to obtain a solution B;
3) pouring the solution B into the solution A for mixing, uniformly dispersing by utilizing ultrasonic waves, pouring the mixed solution into a reaction lining for sealing, placing the lining in an outer kettle for fixing, placing in a homogeneous phase reactor, and heating from room temperature to 185 ℃ under the condition of uniform rotation speed for solvent thermal reaction;
4) after the solvothermal reaction is finished, naturally cooling the reaction kettle to room temperature, taking out a cooled product after the reaction, and collecting the product after alternately cleaning the product by deionized water and alcohol;
5) putting the cleaned product into a watch glass, putting the watch glass into a vacuum drying oven, drying the product at the temperature of 60 ℃, and collecting the product after drying to obtain the three-dimensional pure-phase cobalt sulfide nano microsphere material which is Co9S8A material.
In the step 1), cobalt sources in the reaction raw materials only adopt cobalt acetate tetrahydrate, sulfur sources only adopt thioacetamide, and ethylene glycol is used as a reaction solvent.
The order of addition of the reactants of step 1) is to add cobalt acetate tetrahydrate and thioacetamide to ethylene glycol simultaneously.
The rotating speed of the magnetic stirring in the step 1) is 600-680 r/min, and the time is 55-65 min.
The solvent for dissolving dopamine hydrochloride in the step 2) is ultrapure water only.
And 2) dissolving dopamine hydrochloride in water easily, and stirring to obtain a clear solution.
The ultrasonic dispersion time in the step 3) is 20-30 min.
The type of the reaction lining used in the step 3) is polytetrafluoroethylene.
The filling ratio of the mixed solution in the step 3) poured into the reaction lining is 55-65%.
The step 3) is heated to 175-185 ℃ from room temperature under the condition of the rotating speed of 5-15r/min, and the hydrothermal reaction lasts for 22-26 h.
And 4) alternately cleaning the mixture for 3 to 6 times by using deionized water and ethanol.
And 4) collecting by adopting a suction filtration mode.
And (3) before the product obtained in the step 5) is put into a vacuum drying oven for drying, sealing the product by using a perforated preservative film, wherein the holes are only uniformly perforated on one circle of the edge.
The vacuum drying time in the step 5) is 11-13 h.
The three-dimensional pure-phase cobalt sulfide nano microsphere material prepared by the method is composed of a three-dimensional hollow spherical structure with the average diameter of 0.5-0.8 mu m, and the three-dimensional spherical structure is composed of nano sheets with the uniform thickness of 20nm through self-accumulation.
Example 1
The method comprises the following steps: taking 1.0g of cobalt acetate tetrahydrate, 0.3g of thioacetamide and 40mL of glycol, putting the three raw materials into a beaker, and stirring for 60min at the rotating speed of 650r/min by using magnetic stirring to obtain a pink turbid solution A;
step two: dissolving 17mg of dopamine hydrochloride in 20mL of ultrapure water, and stirring until a clear solution is obtained to obtain a solution B;
step three: mixing the solution A and the solution B, and performing ultrasonic dispersion for 25 min; pouring the mixed solution into a reaction lining according to the filling ratio of 60%, sealing, placing the lining in an outer kettle, fixing, placing in a homogeneous reactor, and heating from room temperature to 180 ℃ at the rotation speed of 10r/min to perform hydrothermal reaction for 24 hours;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, taking out a cooled product after the reaction, alternately cleaning the product for 5 times by using deionized water and ethanol, and collecting the product by suction filtration;
step five: and (3) placing the cleaned product in a watch glass, and sealing the watch glass by using a perforated preservative film, wherein the holes are uniformly perforated on one circle of the edge. Placing the mixture into a vacuum drying oven, drying the mixture for 12 hours at the temperature of 60 ℃, and collecting the product after drying to obtain the three-dimensional pure-phase cobalt sulfide nano microsphere material which is Co9S8A material.
From FIG. 1, it can be seen that the product prepared in this example is cubic CO9S8The serial number of the card is PDF #02-1459。
It can be seen from fig. 2 and 3 that the product prepared by the embodiment has a three-dimensional spherical structure and is uniformly distributed as a whole. The particle sizes are all in the nanometer range, are in the shape of a sheet, have the thickness of about 20nm, and are mutually crossed to form a three-dimensional spherical structure with the average diameter of 0.5-0.8 mu m.
The product prepared in the example 1 is prepared into a button type sodium ion battery, the multiplying power performance test is carried out under different current densities (0.2A/g, 0.5A/g, 1A/g, 2A/g and 5A/g), the test voltage is 0.01V-3.0V, the test result is shown in figure 4, when the current density is 0.2A/g, the first discharge reaches 602.5mAh/g, and after the current density is subjected to charge-discharge circulation under high current density, the capacity is recovered and stabilized at about 368.4mAh/g when the current density is recovered to 0.2A/g.
Example 2
The method comprises the following steps: taking 0.8g of cobalt acetate tetrahydrate, 0.2g of thioacetamide and 35mL of ethylene glycol, putting the three raw materials into a beaker, and stirring for 55min under the condition that the rotating speed is 600r/min by using magnetic stirring to obtain pink turbid solution A;
step two: dissolving 15mg of dopamine hydrochloride in 15mL of ultrapure water, and stirring until a clear solution is obtained to obtain a solution B;
step three: mixing the solution A and the solution B, and performing ultrasonic dispersion for 20 min; pouring the mixed solution into a reaction inner liner according to a filling ratio of 55%, sealing, placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and heating from room temperature to 175 ℃ at a rotating speed of 8r/min to perform hydrothermal reaction for 22 h;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, taking out a cooled product after the reaction, alternately cleaning the product for 3 times by using deionized water and ethanol, and collecting the product by suction filtration;
step five: and (3) placing the cleaned product in a watch glass, and sealing the watch glass by using a perforated preservative film, wherein the holes are uniformly perforated on one circle of the edge. Placing in a vacuum drying oven, drying at 60 deg.C for 11 hr, drying, and collecting product to obtain three-dimensional pure phase cobalt sulfide nanometer microsphere material (Co)9S8A material.
Example 3
The method comprises the following steps: taking 1.2g of cobalt acetate tetrahydrate, 0.5g of thioacetamide and 45mL of ethylene glycol, putting the three raw materials into a beaker, and stirring for 65min under the condition that the rotating speed is 680r/min by using magnetic stirring to obtain pink turbid solution A;
step two: dissolving 20mg of dopamine hydrochloride in 25mL of ultrapure water, and stirring until a clear solution is obtained to obtain a solution B;
step three: mixing the solution A and the solution B, and performing ultrasonic dispersion for 30 min; pouring the mixed solution into a reaction lining according to a filling ratio of 65%, sealing, placing the lining in an outer kettle, fixing, placing in a homogeneous reactor, and heating from room temperature to 185 ℃ at a rotating speed of 15r/min to perform hydrothermal reaction for 26 h;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, taking out a cooled product after the reaction, alternately cleaning the product for 6 times by using deionized water and ethanol, and collecting the product by suction filtration;
step five: and (3) placing the cleaned product in a watch glass, and sealing the watch glass by using a perforated preservative film, wherein the holes are uniformly perforated on one circle of the edge. Putting the mixture into a vacuum drying oven, drying the mixture for 13 hours at the temperature of 60 ℃, and collecting the product after drying to obtain the three-dimensional pure-phase cobalt sulfide nano microsphere material which is Co9S8A material.
The product obtained by the solvothermal reaction method has smaller particle size, is used as a negative electrode material in a sodium ion battery, has larger specific surface area, is integrally in a three-dimensional porous spherical structure, and reduces Na+The migration distance of the electrolyte increases the electrolyte and Na in the electrode material+The contact area of the electrode is larger, more active sites are provided, and the electrochemical performance is good.
Claims (7)
1. A preparation method of a three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material is characterized by comprising the following steps:
1) adding cobalt acetate tetrahydrate, thioacetamide and ethylene glycol into a container, and stirring to obtain a pink turbid solution A; wherein the mass ratio of the cobalt acetate tetrahydrate to the thioacetamide is (0.8-1.2): (0.2-0.5); the ratio of cobalt acetate tetrahydrate to ethylene glycol is 0.8-1.2 g: 35-45 mL;
2) dissolving dopamine hydrochloride in ultrapure water, and stirring to obtain a solution B;
3) adding the solution B into the solution A, uniformly dispersing by ultrasonic, and carrying out solvothermal reaction for 22-26h in a homogeneous phase reactor at the temperature of 175-185 ℃ in a uniform-speed rotating state; after the solvothermal reaction is finished, washing and drying are carried out to obtain the three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material, wherein the cobalt sulfide is Co9S8(ii) a Wherein the mass ratio of the cobalt acetate tetrahydrate to the dopamine hydrochloride is (0.8-1.2) g: (15-20) mg.
2. The preparation method of the three-dimensional pure-phase cobalt sulfide nanosphere sodium ion battery anode material as claimed in claim 1, wherein the rotation speed of stirring in the step 1) is 600-680 r/min, and the time is 55-65 min.
3. The preparation method of the three-dimensional pure-phase cobalt sulfide nanosphere sodium ion battery anode material according to claim 1, wherein the ratio of dopamine hydrochloride to ultrapure water in the step 2) is 15-20 mg: 15-25 mL.
4. The preparation method of the three-dimensional pure-phase cobalt sulfide nanosphere sodium ion battery anode material according to claim 1, wherein the ultrasonic time in the step 3) is 20-30 min.
5. The preparation method of the three-dimensional pure-phase cobalt sulfide nanosphere sodium ion battery anode material according to claim 1, wherein the rotation speed of uniform rotation in the step 3) is 5-15 r/min.
6. The preparation method of the three-dimensional pure-phase cobalt sulfide nanosphere sodium ion battery anode material as claimed in claim 1, wherein the drying temperature in the step 3) is 60 ℃ and the drying time is 11-13 h.
7. The three-dimensional pure-phase cobalt sulfide nanosphere sodium ion battery anode material prepared by the method of any one of claims 1-6, which is characterized in that: the material is composed of a three-dimensional hollow spherical structure with the average diameter of 0.5-0.8 mu m, and the three-dimensional spherical structure is formed by self-stacking nanosheets with the uniform thickness of 20 nm.
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